CN104250376A - Transparent polyamide composite material and preparation method thereof - Google Patents
Transparent polyamide composite material and preparation method thereof Download PDFInfo
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- CN104250376A CN104250376A CN201310256016.4A CN201310256016A CN104250376A CN 104250376 A CN104250376 A CN 104250376A CN 201310256016 A CN201310256016 A CN 201310256016A CN 104250376 A CN104250376 A CN 104250376A
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Abstract
The invention relates to a transparent polyamide composite material and a preparation method thereof. By utilizing the in-situ polymerization principle and the structure characteristics of aliphatic diacid monomers and alicyclic diamine monomers, an aliphatic diacid monomer and an alicyclic diamine monomer needed for preparation of transparent polyamide are subjected to in-situ polymerization reaction with a laminar silicate, so that the transparent polyamide composite material with the light transmittance of 80% or more in the visible light wavelength scope is prepared. The transparent polyamide composite material is relatively high in mechanical strength. During preparation of the transparent polyamide composite material, the transparent polyamide obtained through polymerization of the aliphatic diacid and the alicyclic diamine has extremely good compatibility with the laminar silicate substance, by changing the relative content of the aliphatic diacid and the alicyclic diamine with the laminar silicate substance, when the transparent polyamide composite material keeps material transparency and the designable refractive index in a certain scope, the mechanical properties of the composite material are effectively improved.
Description
Technical field
The invention belongs to polyamide compoiste material, particularly a kind of transparent polyamide matrix material and preparation method thereof.
Background technology
Transparent polyamide is due to its transparency, it is made to have more obvious advantage in fields such as opticinstrument, precise part, measuring instrument, food product pack and bio-medicals relative to other nylon, therefore the attention of many manufacturers has been subject to for the production of transparent polyamide and exploitation, Koga, the esbablished corporations such as Emser, Degussa have been proposed the transparent polyamide product of multiple series all.
European patent EP 50742, US Patent No. 2696482, US2512606 and German patent DE 1595354, DE3717928 etc. describe the preparation method of multiple transparent nylon.By reporting discovery above, transparent polyamide is a kind of non-crystallizable or incomplete polyamide material of crystallization often, and this makes transparent polyamide, and often mechanical strength can not be too high, but its toughness and solvent resistant corrodibility better.Add nano particle in the polymer, the macromolecular chain of polymkeric substance, by series of physical, the chemical action with nano particle, makes the various performance of polymer composites and polymkeric substance have obvious difference.Monomer needed for transparent polyamide can mix very well with multiple nano particle in water, but some nano particles add as nano silicon, the transparency of meeting remarkably influenced product, contrary layered silicate material in water after fully emulsified, when carrying out home position polymerization reaction with transparent polyamide monomer, can not affect the transparency of polymerization process and product, but mechanical strength improves a lot than single transparent polyamide.Therefore by changing the relative content of stratiform silicate material and transparent polyamide monomer, the object of optimized product performance can just be realized within the specific limits.
Transparent polyamide makes that its intensity is lower but shock resistance is better due to the defect of its crystallization aspect, and adding of layered silicate material serves enhancement to transparent polyamide, the mechanical strength of material is increased, add the crystallization behavior that can not change transparent polyamide in essence simultaneously due to layered silicate material, make product have transparent, refractive index and the regulatable feature of mechanical property.The present invention is by introducing related raw material required in the preparation process of transparent polyamide, itself and layered silicate material are carried out home position polymerization reaction, preparation has synthesized a kind of transparent polyamide matrix material, product is made to have high transparent, while refractive index feature can being designed in certain limit, effectively can control again the mechanical property of material, be a kind of functional type polyamide compoiste material.Related raw material selected in the preparation process of transparent polyamide matrix material is moderate, little to harm, is beneficial to and reclaims and deposit.
Summary of the invention
An object of the present invention is to provide a kind of transparent polyamide matrix material.
Two of object of the present invention is by layered silicate material and aliphatic diacid monomer and alicyclic diamine monomer are carried out home position polymerization reaction, thus provides a kind of preparation method of transparent polyamide matrix material.
The present invention utilizes the feature on the principle of home position polymerization reaction and aliphatic diacid monomer and alicyclic diamine monomer structure, by toxic is very little, hardly home position polymerization reaction is carried out to the prepare aliphatic diacid needed for transparent polyamide and aliphatic diamine monomers and layered silicate of environment, prepared the transparent polyamide matrix material that a kind of light transmission rate in visible wavelength range (390nm ~ 770nm) can reach more than 80%.The composition of the layered silicate material added during by regulating and preparing transparent polyamide matrix material and content, the external appearance characteristic of gained transparent polyamide matrix material can be controlled, while obtaining transparent polyamide matrix material, the mechanical strength of transparent polyamide matrix material can also be significantly improved.Transparent polyamide matrix material of the present invention is in preparation process, in transparent polyamide matrix material, the crystallization rate of transparent polyamide is slow, grain growing difficulty, the grain-size formed is less than visible wavelength, for microlitic structure, and layered silicate material add the crystallization behavior that can not affect material, therefore this matrix material have the transparency and corresponding refractive index.Meanwhile, adding of layered silicate material the mechanical strength of transparent polyamide matrix material is greatly improved.In addition, selected aliphatic diacid monomer and alicyclic diamine monomer, moderate cost, poisons little to human body, can not to environment, and the transparent polyamide matrix material obtained belongs to functional type polyamide compoiste material.
Transparent polyamide matrix material of the present invention is carried out obtaining after home position polymerization reaction through mixed melting by the raw material of following weight part, with the weight part of aliphatic diacid for benchmark, wherein:
In described transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed (light transmission rate of transparent polyamide matrix material in visible wavelength range 390nm ~ 770nm can reach more than 80%).
Described aliphatic diacid select oneself in diacid, pimelic acid, suberic acid, nonane diacid, SA, 11 carbon diacid and dodecanedioic acid one or more.
Described alicyclic diamine is selected from 4,4 '-diamino-dicyclohexyl methyl hydride, 4,4 '-diamino-dicyclohexyl propane, 3, one or more in 3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride and isophorone diamine.
Described molecular weight fine setting agent is selected from the one in phenylformic acid and acetic acid.
Described catalyzer is selected from the one in ortho phosphorous acid and N-vinylcaprolactam.
Described molecular weight regulator is selected oneself the one in diacid and dodecanedioic acid.
Described layered silicate material is selected from one or more in montmorillonite, hectorite, halloysite and beidellite.
The preparation method of transparent polyamide matrix material of the present invention comprises the following steps, with the weight part of aliphatic diacid for benchmark:
(1) the layered silicate material of 0.01 ~ 60 weight part is joined in the deionized water of 100 ~ 1000 weight parts, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then the aliphatic diacid of the uniform dispersion obtained and 100 weight parts, the alicyclic diamine of 60 ~ 100 weight parts, the molecular weight of 0.01 ~ 1 weight part are finely tuned agent, the catalyzer of 0.02 ~ 0.5 weight part and the molecular weight regulator of 5 ~ 30 weight parts and joined in reactor, the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain between 0.2 ~ 0.5MPa;
(3) temperature from ambient of the reactor of step (2) being evenly warming up to temperature in 60 ~ 120 minutes is 180 ~ 230 DEG C, and is incubated 30 ~ 90 minutes, maintains between 1.5 ~ 2MPa by the pressure in reactor simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 ~ 230 DEG C by temperature in 90 ~ 180 minutes, to be warming up to temperature be 260 ~ 300 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 260 ~ 300 DEG C insulation 30 ~ 60 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003 ~ 0.1mbar, and under this pressure continue 1 ~ 4 hour; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2 ~ 0.5MPa by 0.003 ~ 0.1mbar, open the bleeder valve of reactor in reactor, the melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.
The present invention has following features:
(1) in the transparent polyamide matrix material prepared of the present invention, the grain-size of transparent polyamide crystallising part is small, and the outward appearance of transparent polyamide matrix material has the transparency, has within the specific limits and can design refractive index simultaneously.
(2) the present invention is preparing the layered silicate material added in the process of transparent polyamide matrix material, and the mechanical strength of the transparent polyamide matrix material obtained is greatly improved.
(3) transparent polyamide matrix material is in preparation process, after various aliphatic diacid and alicyclic diamine polymerization, the consistency of the transparent polyamide that obtains and layered silicate material is fine, by changing the relative content of aliphatic diacid and alicyclic diamine and layered silicate material, make transparent polyamide matrix material while maintenance material transparent, effectively can improve the mechanical property of matrix material.
(4) aliphatic diacid selected by the present invention, the raw materials such as alicyclic diamine are easy to get, moderate, nontoxic to environment.
Embodiment
Embodiment 1
(1) 0.01g montmorillonite is well dispersed in 100g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion obtained and 115g dodecanedioic acid (15g dodecanedioic acid is wherein molecular weight regulator), 80g4,4 '-diamino-dicyclohexyl methyl hydride, 1g phenylformic acid and 0.5g ortho phosphorous acid join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.5MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 200 DEG C, and is incubated 30 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 200 DEG C by temperature in 140 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.03mbar, and under this pressure continue 1 hour; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.03mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 1.
Table 1
Embodiment 2
(1) 30g halloysite is well dispersed in 1000g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion obtained and 110g dodecanedioic acid (10g dodecanedioic acid is wherein molecular weight regulator), 100g3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride, 0.01g phenylformic acid and 0.02g ortho phosphorous acid join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.3MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 60 minutes temperature is 180 DEG C, and is incubated 30 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 120 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 40 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 1 hour; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 2.
Table 2
Embodiment 3
(1) 30g halloysite is well dispersed in 1000g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion that obtains and 100g dodecanedioic acid, 80g3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride, 5g hexanodioic acid (molecular weight regulator), 1g phenylformic acid and 0.5g ortho phosphorous acid join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 180 DEG C, and is incubated 30 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 90 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 50 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 2 hours; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 3.
Table 3
Embodiment 4
(1) 20g hectorite is well dispersed in 500g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion that obtains and 80g dodecanedioic acid, 20g suberic acid, 100g3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride, 0.5g phenylformic acid, 0.5g ortho phosphorous acid and 15g hexanodioic acid (molecular weight regulator) join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 180 DEG C, and is incubated 30 minutes, the pressure in reactor is maintained 2MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 90 minutes, to be warming up to temperature be 260 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 260 DEG C insulation 60 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 4 hours; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.4MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 4.
Table 4
Embodiment 5
(1) 20g hectorite is well dispersed in 500g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion that obtains and 80g dodecanedioic acid, 20g suberic acid, 100g3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride, 0.5g phenylformic acid, 0.5g ortho phosphorous acid and 15g hexanodioic acid (molecular weight regulator) join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.4MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 230 DEG C, and is incubated 60 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 230 DEG C by temperature in 120 minutes, to be warming up to temperature be 300 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 300 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 3 hours; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.3MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 5.
Table 5
Embodiment 6
(1) 30g beidellite is well dispersed in 500g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion that obtains and 100g SA, 100g4,4 '-diamino-dicyclohexyl methyl hydride, 0.01g phenylformic acid, 0.02g ortho phosphorous acid and 30g hexanodioic acid (molecular weight regulator) join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain between 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 180 DEG C, and is incubated 30 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 120 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 1 hour; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by DXL-10000 and the XJ-300A impact test instrument drawing machine of capital technological constraints platform, its mechanical strength is characterized, the results are shown in Table 6.
Table 6
Embodiment 7
(1) 0.01g halloysite is well dispersed in 100g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion that obtains and 100g SA, 60g3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride, 40g isophorone diamine, 0.1g phenylformic acid, 0.5g ortho phosphorous acid and 20g hexanodioic acid (molecular weight regulator) join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain between 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 220 DEG C, and is incubated 90 minutes, the pressure in reactor is maintained 1.8MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 220 DEG C by temperature in 120 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 2 hours; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 7.
Table 7
Embodiment 8
(1) 24g halloysite is well dispersed in 500g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion that obtains and 100g hexanodioic acid, 60g4,4 '-diaminocyclohexyl propane, 0.05g phenylformic acid, 0.05gN-vinylcaprolactam and 5g hexanodioic acid (molecular weight regulator) join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain between 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 120 minutes temperature is 180 DEG C, and is incubated 30 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 180 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003mbar, and under this pressure continue 1 hour; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.003mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 8.
Table 8
Embodiment 9
(1) 60g montmorillonite is well dispersed in 1000g deionized water, after being fully uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then by the uniform dispersion obtained and 120g dodecanedioic acid (20g dodecanedioic acid is wherein molecular weight regulator), 80g4,4 '-diamino-dicyclohexyl methyl hydride, 1g phenylformic acid and 0.5g ortho phosphorous acid join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 180 DEG C, and is incubated 70 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 120 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.1mbar, and under this pressure continue 1 hour.Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.1mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide compoiste material melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.In gained transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide matrix material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide matrix material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide matrix material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform, its mechanical strength is characterized, the results are shown in Table 9.
Table 9
Comparative example
(1) by 1000g deionized water, 120g dodecanedioic acid (20g dodecanedioic acid is wherein molecular weight regulator), 80g4,4 '-diamino-dicyclohexyl methyl hydride, 1g phenylformic acid and 0.5g ortho phosphorous acid join in reactor, and the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process 3 ~ 5 times to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain 0.2MPa;
(3) open heating unit, the temperature from ambient of reactor being evenly warming up in 90 minutes temperature is 180 DEG C, and is incubated 70 minutes, the pressure in reactor is maintained 1.5MPa simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 DEG C by temperature in 120 minutes, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 280 DEG C insulation 30 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.1mbar, and under this pressure continue 1 hour.Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2MPa by 0.1mbar, open the bleeder valve of reactor in reactor, the water white transparency polyamide melt of outflow obtains transparent polyamide material after ice-water bath quenching.The crystallising part of gained transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.The light transmission rate of transparent polyamide material in visible wavelength range (390nm ~ 770nm) is more than 80%.
The transparent polyamide material prepared is the homogeneous melt of water white transparency when temperature is 280 DEG C, is colourless transparent material after quenching.With the uv transmittance of the LIV-1601PC ultraviolet-visible pectrophotometer test transparent polyamide material of Japanese Shimadzu Corporation, by HTC-100 ellipsometer test, its refractive index is measured, by the DXL-10000 drawing machine of capital technological constraints platform and XJ-300A impact test instrument, its mechanical strength is characterized, the results are shown in Table 10.
Table 10
Can find out by comparative example and embodiment 9 are carried out contrast, owing to not adding layered silicate material in comparative example, its refractive index and mechanical strength are not so good as the good of embodiment 9, and uv transmittance is substantially identical.
Claims (9)
1. a transparent polyamide matrix material, is characterized in that: described transparent polyamide matrix material is carried out obtaining after home position polymerization reaction through mixed melting by the raw material of following weight part, with the weight part of aliphatic diacid for benchmark, wherein:
2. transparent polyamide matrix material according to claim 1, is characterized in that: in described transparent polyamide matrix material, the crystallising part of transparent polyamide is that the crystal grain being less than visible wavelength by grain-size is formed.
3. transparent polyamide matrix material according to claim 1, is characterized in that: described aliphatic diacid select oneself in diacid, pimelic acid, suberic acid, nonane diacid, SA, 11 carbon diacid and dodecanedioic acid one or more.
4. transparent polyamide matrix material according to claim 1, it is characterized in that: described alicyclic diamine is selected from 4,4 '-diamino-dicyclohexyl methyl hydride, 4,4 '-diamino-dicyclohexyl propane, 3, one or more in 3 '-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride and isophorone diamine.
5. transparent polyamide matrix material according to claim 1, is characterized in that: described molecular weight fine setting agent is selected from the one in phenylformic acid and acetic acid.
6. transparent polyamide matrix material according to claim 1, is characterized in that: described catalyzer is selected from the one in ortho phosphorous acid and N-vinylcaprolactam.
7. transparent polyamide matrix material according to claim 1, is characterized in that: described molecular weight regulator is selected oneself the one in diacid and dodecanedioic acid.
8. transparent polyamide matrix material according to claim 1, is characterized in that: described layered silicate material is selected from one or more in montmorillonite, hectorite, halloysite and beidellite.
9. a preparation method for the transparent polyamide matrix material described in claim 1 ~ 8 any one, is characterized in that, described preparation method comprises the following steps: with the weight part of aliphatic diacid for benchmark,
(1) the layered silicate material of 0.01 ~ 60 weight part is joined in the deionized water of 100 ~ 1000 weight parts, after being uniformly mixed, the dispersion liquid obtained being joined in mulser and carries out emulsification, obtain water white uniform dispersion; Then the aliphatic diacid of the uniform dispersion obtained and 100 weight parts, the alicyclic diamine of 60 ~ 100 weight parts, the molecular weight of 0.01 ~ 1 weight part are finely tuned agent, the catalyzer of 0.02 ~ 0.5 weight part and the molecular weight regulator of 5 ~ 30 weight parts and joined in reactor, the agitator opening reactor stirs;
(2) reactor of airtight step (1), carries out inflated with nitrogen to reactor and vacuumizes process to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactor maintain between 0.2 ~ 0.5MPa;
(3) temperature from ambient of the reactor of step (2) being evenly warming up to temperature in 60 ~ 120 minutes is 180 ~ 230 DEG C, and is incubated 30 ~ 90 minutes, maintains between 1.5 ~ 2MPa by the pressure in reactor simultaneously; Then continue reacting by heating still, making the temperature of reactor be 180 ~ 230 DEG C by temperature in 90 ~ 180 minutes, to be warming up to temperature be 260 ~ 300 DEG C, during this period, at the uniform velocity reduces pressure in reactor to normal pressure, and get rid of the gaseous matter in reactor; Temperature be 260 ~ 300 DEG C insulation 30 ~ 60 minutes after, open vacuum pump, the pressure drop in reactor be low to moderate 0.003 ~ 0.1mbar, and under this pressure continue 1 ~ 4 hour; Stop stirring, be filled with nitrogen, make the pressure in reactor be increased to 0.2 ~ 0.5MPa by 0.003 ~ 0.1mbar, open the bleeder valve of reactor in reactor, the melt of outflow obtains transparent polyamide matrix material after ice-water bath quenching.
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